Pigment dyes



United States Patent 3,376,298 PIGMENT DYES Willy Braun, Heidelberg, and Rolf Mecke, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fahrilr Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Apr. 6, 1964, Ser. No. 357,797 Claims priority, application Germany, Apr. 26, 1963,

4 Claims. (Cl. 260244) This invention relates to new organic pigment dyes.

Among the many requirements which the properties of organic pigment dyes must satisfy, high color strength, high fastness to light and good solvent fastness are particularly important. Moreover it is required of organic pigments, particularly those of the yellow series, that they should have the smallest possible tendency to become darker. Prior art yellow to red organic pigments leave much to be desired as regards these high requirements. There is therefore a demand for yellow to red pigments which will have the said properties in a high degree.

The object of this invention is to provide new valuable pigment dyes which are distinguished by high color strength, high fastness to light and very good solvent fastness and of which even the yellow dyes have only very slight tendency to become darker. The preferred pigment dyes have the general formula:

in which one X denotes a NH bridge and the other X and Z denote the bridge member NH--, O or S-, the radicals A and G condensed onto the rings B and F denote aromatic of heterocyclic radicals consisting of one or more rings and in which the rings A, D and G may bear substituents.

Pigment dyes having the general formula:

divalent aromatic radical, such as a radical having one of the formulae:

and G denotes a divalent aromatic radical, such as a radical having one of the formulae:

a O@H. NO2 93a (l V0 N Ha1 Hal l C l D I E Hal N N Hal with a compound having the formula:

III IV or, when both X and Z in Formula I denote NH-, by condensing a 2,3-dihaloquinoxaline having the formula:

N N Hal Hal A B I: or F) o E N// Hal Hal N V VI with the compound:

VII

" Hal in Formulae II, V and VI denoting a halogen atom,

preferably a chlorine atom or bromine atom.

The process may be carried out so that 2,3,7,8-tetrahalopyrazino-[2,3-g]-quinoxalines which may bear substituents in 5- and/or lfl-position, for example Ilitro groups, amino groups, acylamino groups, sulfonamide groups, alkyl groups, such as methyl groups, alkoxy groups, such as methoxy groups, or halogen atoms, such as chlorine atoms, are used as derivatives of 2,3-dihaloquinoxalines, and aromatic or heterocyclic amino compounds which bear in ortho-position to the amino group a further amino group, a hydroxyl group or a sulfhydryl group (examples are 1,2-diamino, 1,2-aminohydroxy and/or 1,2-aminomercapto compounds) are used as reactants. The aromatic or heterocyclic 1,2-diamino, 1,2- aminohydroxy and 1,2-amirlomercapto compounds may consist of one or more rings. The following are suitable 3 for example: o-diamino, o-aminohydroxy and o-amino mercapto derivatives of benzene, phenazine, phenoxazine, quinoxaline or of anthraquinone, which may contain other substituents, for example nitro groups, amino groups, acylamino groups, such as acetyl- 5 advantageous to use solvents or diluents of high boiling amino or benzoylamino groups, sulfonamide groups, alkyl point which do not react under the conditions of the regroups, such as methyl groups or ethyl groups, alkoxy action, such as nitrobenzene or chlorinated benzenes. groups, such as methoxy groups, or halogen atoms, such Dialkyl carboxylic amides, such as dimethylformamide as chlorine atoms or bromine atoms. The following are or i -met'nylpyrrolidone, are particularly suitable. specific examples of these compounds: o-phenylene di- Since hydrogen halide is formed in the condensation, amine, l,2-diamino-4-chlorobenzene, o-aminophenol, 2- it is often advantageous to add acid-binding agents to the amino-4-chlorophenol, l-amino-Z-mercapto-4-methoxyreaction mixture. Organic or inorganic bases may be benzene, Z-amino-3-hydroxynaphthalene, 2,3-diaminoanused as acid-binding agents. Examples are alkalimetal thraquinone, Z-amino-3-hydroxyquinoxaline, 2,3-diarninocarbonates or alkaline earth metal carbonates, such as phenazine, 2-amino-3-hydroxyphenazine, Z-amino- 3 -hy- 5 sodium carbonate, potassium carbonate, sodium hydrodroxyphenazine, 2-amino-3-hydroxyphenoxazine, 2,3-digen carbonate, potassium hydrogen carbonate or magnesiaminoquinoxaline and 2-amino-3-mcrcaptoquinoxaline. um carbonate. Aliphatic, aromatic or heterocyclic tertiary The condensation for the production of the new dyes amines, such as tripropylamine, tri-n-butylamine, N,N- is advantageously carried out by reacting the said 2,3,7,8- dimethylaniline, pyridine or quinoline, are also suitable. tetrahalopyrazine- [2,3 gl-quinoxalines, preferably the Instead of an acid-binding agent being added, it is also tetrachloro derivative, with about twice the molar amount possible to use an excess of the o-diamino, o-arninohyof the said aromatic or heterocyclic 1,2-diamino, 1,2- droxy or o-aminomercapto compound used, the amino aminohydroxy or 1,2-aminomercapto compounds in the groups of the substance added in excess thus binding the presence of organic solvents and/ or diluents and if neceshydrohalic acid liberated. Finally in some cases the addisary in the presence of acid-binding agents at temperation of an acid-binding agent may be wholly dispensed tures of 60 to 200 C. with. The hydrohalic acid liberated then either escapes in When twice the molar amount (with reference to the gaseous form or dissolved in the solvent or diluent. tetrahalopyrazino-[2,3-g]-quinoxaline used) of the same The condensation proceeds generally in the temperaamino compound is used, compounds having the general ture range from 60 to 200 C. It is preferably to choose Formula I are obtained in which both bridging groups X temperatures of from 100 to 200 -s but the Condensaand Z are the same and the radicals A and G are the tion takes place in some cases, for example when using same. o-aminomercapto compounds, at temperatures of 60 to The condensation may however also be carried out by 100 C. The condensation products are insoluble or. first reacting 2,3,7,8-tetrahalopyrazino-[2,3-g1-quinoxsparingly soluble in organic solvents. They may therealine with only about the molar amount of an aromatic fore be separated from the cooled reaction mixture by or heterocyclic amino compound of the above-mentioned simple filtration. To purify them, they may be boiled up type in the manner described above and then reacting with organic solvents or precipitated from sulfuric acid the condensation product formed, which need not be solution by dilution with water. isolated, with another about molar equivalent of another 2,3,7,8 -tetrachloropyrazino-[2,3-g1-quinoxaline to be aromatic or heterocyclic amino compound of the above- 4 used as initial material for the process of this invention mentioned type. Compounds are then obtained having may be obtained by reaction of 1,2,4,5-tetraaminobenzene the general Formula I in which one bridging group X is with oxalic acid in aqueous hydrochloric acid solution different from Z and/or the radicals A and G are ditferand subsequent treatment of the product obtained with cut from each other. chlorinating agents, such as phosphorus pentachloride, Compounds of the general Formula I in which both phosphorus oxychloride, ,phosgene or thionyl chloride. groups X and Z denote -NH- may also be obtained The course of the reaction is illustrated by the following by the process according to this invention by reacting equation:

1 HiN- NH: HO I\\ on +2(COOH)1= +4Hz0 um um HO \N/ \N/ 011 +41 C15 J: +POC1+4HCI no \N/ \N/ or \\N/ 01 under the above-mentioned conditions a 2,3-di-haloquinoxaline which may contain substituents in 5-, 6-, 7- The dyes obtainable according ,to this invention have and/or 8-position, for example nitro groups, amino n5 vivid brightness, great color strength and outstanding groups, acylamino groups, such as acetylarnino groups or fastness properties. They are eminently useful as yellow benzoylamino groups, sulfonamido groups, alkyl groups, to bluish red pigment dyes for coloring plastics and such as methyl groups or ethyl groups, alkoxy groups, lacquers and for paints and printing pastes. such as methoxy groups, or halogen atoms, such as Several tautomeric forms of the Formula I are conchlorine atoms or bromine atoms, or condensed-on aroceivable. Thus for example by reacting two moles of 1,2- matic or heterocyclic rings, with about half the molar diaminobenzene with one. mole of 2,3,7,8-tetrachloroamount of l,2,4,5-tetraaminobenzene which may contain pyrazino-[2,3-g]-quinoxaline, the same product is obsubstituents, for example nitro groups, amino groups, tained as by the reaction of two moles of 2,3-di-chloroacylamino groups, sulfonamido groups, alkyl groups, quinoxaline with one mole of 1,2,4,S-tetraaminobenzene. such as methyl groups, alkoxy groups, such as methoxy It is also conceivable that the compounds obtainable by naphthalene, authracene, H

position and/or in groups, or halogen atoms, such as chlorine atoms, in 3- 6-pos ition.

The process according to this invention is carried out in the presence of organic solvents and/or diluents. It is the process of this invention may be present as mixtures of the two possible isomers Ia and Ib:

200 parts of the tetrahydrochloride of 1,2,4,5-tetraaminobenzene is boiled for one hour in 2000 parts of hydrochloric acid with 193 parts of oxalic acid. After the whole has been cooled, the precipitate is suction filtered and washed with water. 160 parts of 2,3,7,8-tetrahydroxypyrazino-[2,3-g]-quinoxaline is obtained in the form of small needles which decompose above 300 C. without melting.

100 parts of 2,3,7,8-tetrahydroxypyrazino [2,3-g]-quinoxaline is slowly heated in 500 parts of nitrobenzene with 445 parts of phosphorus pentachloride to 150 C. in the course of an hour, the phosphorus oxychlorideformed being distilled off through a descending condenser. After a total of two hours, the mixture is cooled. The residue is suction filtered and washed with benzene. 93 parts of 2,3,7,8 tetrachloropyrazino [2,3-g] quinoxaline is obtained as pale yellowish needles which melt at 315 to 316 C.

32 parts of 2,3,7,8-tetrachloropyrazino-[2,3-g]-quinoxaline is stirred with 22 parts of o-phenylene diamine and 49 parts of N,N-dimethylaniline in 350 parts of N- methylpyrrolidone for two hours at 200 C. After the whole has been cooled, the residue is filtered off and washed with methanol. 36 parts of a red dye having the Examples 2 to 5 is obtained.

By using corresponding amounts of the o-diamines specified in the following table instead of 22 parts of o-phenylene diamine and otherwise proceeding as described in Example 1, dyes having analogous constitution are obtained having the shades indicated in the table.

Example 6 28.4 parts of the tetrahydrochloride of l,2,4,5-tetraaminobenzene is stirred with 40 parts of 2,3-dichlor0- quinoxaliue and 115 parts of tripropylamine in 400 parts of N-methylpyrrolidone under nitrogen for two hours at 160 to 170. The whole is cooled and the residue is filtered off and washed with methanol. 30 parts of a red dye is obtained which is identical with the dye obtainable according to Example 1.

Example 7 32 parts of 2,3,7,8-tetrachloroquinoxalino-[2,3-g1-pyrazine is stirred for two hours at C. with 22 parts of o-aminophenol and 17.5 parts of sodium hydrogen carbonate in 300 parts of dimethylformamide. The whole is cooled and the residue is filtered off and washed with methanol and water. 32 parts of a yellow dye having the constitution:

is obtained.

Examples 8 to 11 By following the procedure described in Example 7 but using equivalent amounts of the o-aminohydroxy compounds specified in the following table instead of 22 parts of o-aminophenol, dyes having an analogous constitution are obtained having the shades specified in the table:

TABLE Example o-Amlnohydroxy compound Color 8 2-amino-4-chloroplienyl 9 2-amino-3-hydroxynaphthalene 10 2-amino-3-hydroxyauthraquinon 11 2-an1ino-3-liydroxyquiuoxalme...

Example 12 s N N s Examples 13 to 16 By following the procedure described in Example 12 but using equivalent amounts of the o-aminomercapto compounds specified in the following table instead of 25 parts of o-aminothiophenol, dyes having analogous constitution are obtained having the shades given in the table:

TABLE Example o-Aminom ercapto compound Color 1 l-aminoQ-rnercaptoA-chlorobenzene BllllSll red. 14. 1-amiuo2-1nercapto-4-metho ybenzenet. Do. 15.. 1--\mino2-mercaptoi-benzoylamino- D0.

benzene. 16 2-amino 3-mercaptonaphthalene D0.

Example 17 32 parts of 2,3,7,8-tetrachloropyra2ino-[2,3-g]-quinoxaline and 11 parts of o-phenylene diamine are stirred in 300 parts of dimethylformamide for two hours at 150 C. Then 12.5 parts of o-aminothiophenol is added and the whole heated for another hour at 150 C. The whole is cooled and the residue suction filtered and washed with methanol. 36 parts of a red dye is obtained having the constitution:

7 Example 18 32 parts of 2,3,7,S-tetrachloropyrazino-[2,3-g]-quinoxaline and 22 parts of o-aminophenol are heated in 350 parts of o-dichlorobenzene for one hour at 170 C. The Whole is cooled and the residue is filtered off and washed with benzene and methanol. 35 parts of a yellow compound is obtained having the constitution:

35 parts of this intermediate product is heated with 12.5 parts of o-aminothiophenol in 300 parts of dimethylformamide for one hour at 120 C. The Whole is cooled and the residue is filtered off and washed with methanol.

35 parts of a red dye is obtained having the constitution:

wherein Y and Z each represent a bridge member selected from the group consisting of -NH, O and S, R and R each represent a substituent selected from the group consisting of H, Cl, -OCH NO and benzoylarnino with the proviso that at least one of said R and R is hydrogen, and wherein R and R taken together may further represent a divalent radical selected 1 from the class consisting of 2. The dye of the formula:

3. The dye of the formula:

H H T s O 4. The .dye of the formula:

UNITED STATES PATENTS 3,006,917 10/1961 Seeger 260-244 JOHN D. RANDOLPH, Primary Examiner. WALTER A. MODANCE, Examiner. R. T. BOND, .AssistanrExaminer. 

1. A DYE OF THE FORMULA
 3. THE DYE OF THE FORMULA: 